Picosecond sulfur K-edge X-ray absorption spectroscopy with applications to excited state proton transfer

Picosecond X-ray absorption (XA) spectroscopy at the S K-edge (∼2.4 keV) is demonstrated and used to monitor excited state dynamics in a small organosulfur molecule (2-Thiopyridone, 2TP) following optical excitation. Multiple studies have reported that the thione (2TP) is converted into the thiol (2...

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Published inStructural dynamics (Melville, N.Y.) Vol. 4; no. 4; p. 044021
Main Authors Van Kuiken, Benjamin E., Ross, Matthew R., Strader, Matthew L., Cordones, Amy A., Cho, Hana, Lee, Jae Hyuk, Schoenlein, Robert W., Khalil, Munira
Format Journal Article
LanguageEnglish
Published United States American Institute of Physics, Inc 01.07.2017
American Crystallographic Association/AIP
American Crystallographic Association
AIP Publishing LLC and ACA
Subjects
Absorption spectroscopy
Acetonitrile
Decay
Density functional theory
Equilibrium
Excitation
Experiments
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Lasers
Ligands
MATERIALS SCIENCE
Photochemical reactions
Photoexcitation
Response time
Solvents
Sulfur
Time dependence
Ultrafast Structural Dynamics—A Tribute to Ahmed H. Zewail
X ray absorption
X-ray spectroscopy
X-rays
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Summary:Picosecond X-ray absorption (XA) spectroscopy at the S K-edge (∼2.4 keV) is demonstrated and used to monitor excited state dynamics in a small organosulfur molecule (2-Thiopyridone, 2TP) following optical excitation. Multiple studies have reported that the thione (2TP) is converted into the thiol (2-Mercaptopyridine, 2MP) following photoexcitation. However, the timescale and photochemical pathway of this reaction remain uncertain. In this work, time-resolved XA spectroscopy at the S K-edge is used to monitor the formation and decay of two transient species following 400 nm excitation of 2TP dissolved in acetonitrile. The first transient species forms within the instrument response time (70 ps) and decays within 6 ns. The second transient species forms on a timescale of ∼400 ps and decays on a 15 ns timescale. Time-dependent density functional theory is used to identify the first and second transient species as the lowest-lying triplet states of 2TP and 2MP, respectively. This study demonstrates transient S K-edge XA spectroscopy as a sensitive and viable probe of time-evolving charge dynamics near sulfur sites in small molecules with future applications towards studying complex biological and material systems.
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USDOE Office of Science (SC), Basic Energy Sciences (BES)
AC02-05CH11231; SC0002190; AC02-76SF00515
Present address: Center for Inorganic Analysis, Division of Metrology for Quality of Life, Korea Research Institute of Standards and Science, Daejeon 34113, South Korea.
Present address: PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, CA 94025, USA.
Author to whom correspondence should be addressed. Electronic mail: mkhalil@uw.edu.
Present address: Pohang Accelerator Laboratory, San-31 Hyoja-dong Pohang, Kyungbuk 37673, Republic of Korea.
Present address: SLAC National Accelerator Laboratory, Menlo Park, CA 94025, USA.
Present address: Max-Planck Institute for Chemical Energy Conversion, Stiftstrasse 34−36, D−45470 Muülheim an der Ruhr, Germany.
Present address: Linac Coherent Light Source, SLAC National Accelerator Laboratory, Menlo Park, CA 94025, USA.
ISSN:2329-7778
2329-7778
DOI:10.1063/1.4983157